Mapping sub-surface structure of thin films in three dimensions with an optical near-field

Subsurface mapping is crucial to understanding many biological systems as well as structured thin films for (opto)electronic or photonic applications. A non‐invasive method is presented to map subsurface nanostructures from scanning near‐field optical microscopy images. The Bethe–Bouwkamp model is used to simulate imaging of buried nano‐objects or subsurface slanted planar interfaces, and it is shown how to determine their depth and size, or the interface inclination, from just one image. It is shown that the steep optical field gradient makes near‐field microscopy a particularly sensitive depth probe for thin films

Tuning Fullerene Intercalation in a Poly (thiophene) derivative by Controlling the Polymer Degree of Self-Organisation

Controlling the nanoscale arrangement in polymer-fullerene organic solar cells is of paramount importance to boost the performance of such promising class of photovoltaic diodes. In this work, we use a pseudo-bilayer system made of poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), to acquire a more complete understanding of the diffusion and intercalation of the fullerene-derivative within the polymer layer. By exploiting morphological and structural characterisation techniques, we observe that if we increase the film solidification time the polymer develops a higher crystalline order, and, as a result, it does not allow fullerene molecules to intercalate between the polymer side-chains. Gaining insight into the detailed fullerene intercalation mechanism is important for the development of organic photovoltaic diodes (PVDs)

Neutron polarisation analysis of Polymer: Fullerene blends for organic photovoltaics

The photogeneration process in polymer-fullerene organic solar cells relies strongly on the nanostructure and on the nano/picosecond dynamics occurring in these complex blends. Elastic and inelastic neutron scattering techniques are valuable tools with which to investigate those features in the appropriate time and space domains. In particular, quasi-elastic neutron scattering (QENS) connects useful structural and dynamical information by the measurement of dynamical incoherent (single particle) fluctuations in soft materials as a function of lengthscale. Extraction of these fluctuation rates can, however, be hampered by the presence of coherent contributions, originating from elastic scattering, and/or inelastic scattering modes which overlap in the space/time domain with the incoherent single-particle motions. As we have already seen in a previous study [1], this happens in poly(3-hexylthiophene) (P3HT) and [6,6]-Phenyl C61 butyric acid methyl ester (PCBM) solid blends, in which the coherent contribution arising from the PCBM crystalline phase seems to affect the interpretation of the polymer dynamics. Here, we utilise neutron polarisation analysis as an effective tool to separate coherent and incoherent contributions and make QENS data analysis of these blends more reliable

Low-Temperature Photoluminescence Spectroscopy of Solvent-Free PCBM Single-Crystals

PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) is a highly soluble C60 derivative that is extensively used in organic solar cells, enabling power conversion efficiencies above 10%. Here we report, for the first time to the best of our knowledge, the photoluminescence of high-quality solvent-free PCBM crystals between room temperature and 4 K. Interestingly, the PL spectra of these crystals become increasingly structured as the temperature is lowered, with extremely well-resolved emission lines (and a minimum line width of ∼1.3 meV at 1.73 eV). We are able to account for such a structured emission by means of a vibronic coupling model including Franck–Condon, Jahn–Teller and Herzberg–Teller effects. Although optical transitions are not formally forbidden from the low-lying excited states of PCBM, the high symmetry of the electronically active fullerene core limits the intensity of the 0–0 transition, such that Herzberg–Teller transitions which borrow intensity from higher-lying states represent a large part of the observed spectrum. Our simulations suggest that the emissive state of PCBM can be considered as a mixture of the T1g and Hg excited states of C60 and hence that the Hg state plays a larger role in the relaxed excited state of PCBM than in that of C60

Enhanced crystallinity and film retention of P3HT thin-films for efficient organic solar cells by use of preformed nanofibers in solution

We report the preparation of films of poly(3-hexylthiophene) nanofibers suitable for fabrication of efficient multilayer solar cells by successive deposition of donor and acceptor layers from the same solvent. The nanofibers are obtained by addition of di-tert-butyl peroxide (DTBP) to a solution of P3HT in chlorobenzene. Interestingly, by varying the concentration of DTBP we are able to control both crystallinity and film retention of the spin-cast films. We also investigate the influence of the DTBP-induced crystallization on charge transport by thin-film transistor measurements, and find a more than five-fold increase in the hole mobility of nanofiber films compared to pure P3HT. We attribute this effect to the synergistic effects of increased crystallinity of the fibers and the formation of micrometer-sized fiber networks. We further demonstrate how it is possible to make use of the high film retention to fabricate photovoltaic devices by subsequent deposition of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) from a chlorobenzene solution on top of the nanofiber film. The presence of a relatively large crystalline phase strongly affects the diffusion behavior of PCBM into the P3HT film, resulting in a morphology which is different from that of common bulk heterojunction solar cells and resembles a bilayer structure, as can be inferred from comparison of the external quantum efficiency spectra. However, a high power conversion efficiency of 2.3% suggests that there is still a significant intermixing of the two materials taking place

Ultrathin, Ultra‐Conformable, and Free‐Standing Tattooable Organic Light‐Emitting Diodes

A novel tattooable, ultrathin, green organic light‐emitting diode (OLED) fabricated on top of commercial temporary tattoo paper, is demonstrated. The transfer mechanism relies on dissolution of the sacrificial layer typically incorporated in paper‐tattoos. The ready‐to‐use device can be stored on the tattoo substrate and released on the target surface at a later time, simply by a slight wetting of the tattoo paper with water. This approach provides a quick and easy method of transferring OLEDs on virtually any surface. This is particularly appealing, in perspective, for on‐skin and disposable electronic applications. The proof of concept demonstrates, for the very first time, the feasibility of ultrathin operational OLED tattoos. While the performance of such devices is not yet comparable with that of OLEDs on rigid or flexible non‐tattooable substrates, the results show the potential for an OLED tattoo technology in integrated conformable electronic circuits

Sub-wavelength focusing of high intensities in microfibre tips

Sub-wavelength efficient intensity confinement has been demonstrated in nanostructured optical microfibre tips. Focus Ion Beam (FIB) milling was used to nanostructure gold-coated optical microfibre tips and form apertures at the apex. Simulations were carried out to optimize the device design. Enhanced transmission efficiency (higher than 10-2) was achieved in spot sizes of ~λ/10. Nanostructured microfibre tips have the potential for a number of applications including optical recording, photolithography and scanning near-field optical microscopy (SNOM)